Preparation of high specific surface area Cu(OH)2 nanowires/nanorods by coordinated precipitation
Shuang XU1,2, Jingkui QU1*, Guangye WEI1, Tao QI1
1. National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
2. School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
Abstract:Nano-copper hydroxide powder with different morphologies was synthesized by coordinated precipitation using CuSO4?5H2O, ammonia and NaOH as materials. The effects of amounts of NaOH and ammonia, and CuSO4 concentration on the morphology, particle size and specific surface area were investigated. The results showed that for different amounts of NaOH, when CuSO4 initial concentration was 0.1 mol/L, molar ratio of NH3:CuSO4=7 and molar ratio of NaOH:CuSO4=2~4, the prepared Cu (OH)2 was assembled into flower clusters by nanowires, and the numbers of flower-like structure of single head decreased and the double head flowers increased with amounts of NaOH increasing. For different amounts of ammonia, when CuSO4 initial concentration was 0.1 mol/L, molar ratio of NH3:NaOH=2 and molar ratio of NH3:CuSO4=7, the flower-like copper hydroxide of which the diameter was 0.3?1 μm and the length was 1?3 μm composed of nanowires the aspect ratio of which was 20?60 was obtained, and the Cu(OH)2 particles the surface on which had adsorbed water had uniform particle size distribution and the specific surface area of the powder was as large as 83.3 m2/g. For CuSO4 concentration, when molar ratio of NH3:CuSO4=3, and molar ratio of NaOH:CuSO4=2, the Cu(OH)2 nanowires tended to assemble into flower-like cluster structures with CuSO4 initial concentration decreasing.
徐爽 曲景奎 魏广叶 齐涛. 配位沉淀制备高比表面积氢氧化铜纳米线/纳米棒[J]. 过程工程学报, 2018, 18(5): 1052-1060.
Shuang XU Jingkui QU Guangye WEI Tao QI. Preparation of high specific surface area Cu(OH)2 nanowires/nanorods by coordinated precipitation. Chin. J. Process Eng., 2018, 18(5): 1052-1060.
[1] Oswald H R, Reller A, Schmalle H W, et al.Structure of Copper(II) Hydroxide, Cu(OH)2 [J]. Acta Crystallogr. C 1990, 46: 2279?2284.
[2] 白培万, 孙金全, 吴秀春.纳米氢氧化铜可湿性粉剂的合成 [J]. 太原理工大学学报, 2008, (02): 164?166.
[3]Bai P W, Sun J Q, Wu X C.Synthesis and Characterization of Nano-copper Hydroxide Wettable Power [J]. Journal of Taiyuan University of Technology, 2008, (02): 164?166.
[4] Zhao L J, Ortiz C, Adeleye A S, et al.Metabolomics to Detect Response of Lettuce (Lactuca Sativa) to Cu(OH)2 Nanopesticides: Oxidative Stress Response and Detoxification Mechanisms [J]. Environ. Sci. Technol., 2016, 50: 9697?9707.
[5] Gurav K V, Patil U M, Shin S W, et al.Room Temperature Chemical Synthesis of Cu(OH)2 Thin Films for Supercapacitor Application [J]. J. Alloy. Compd., 2013, 573: 27?31.
[6] Lei S J, Liu Y, Fei L F, et al.Commercial Dacron Cloth Supported Cu(OH)2 Nanobelt Arrays for Wearable Supercapacitors [J]. J. Mater Chem. A, 2016, 4: 14781?14788.
[7] Zhou X S, Luo Z H, Tao P F, et al.Facile Preparation and Enhanced Photocatalytic H2-production Activity of Cu(OH)2 Nanospheres Modified Porous g-C3N4 [J]. Mater. Chem. Phys., 2014, 143: 1462?1468.
[8] Shi H X, Zhao Y X, Li N, et al.Synthesis and Photocatalytic Activity of Novel CuO Cauliflowers Grown from Cu(OH)2 [J]. Catal. Commun., 2014, 47: 7?12.
[9] Mosaddegh E, Hassankhani A, Karimi-Maleh H.Synthesis and Characterization of ES/Cu(OH)2 Nanocomposite: A Novel and High Effective Catalyst in the Green Synthesis of Pyrano[4, 3-b]pyrans [J]. Mat. Sci. Eng. C-mater., 2015, 46: 264?269.
[10] Fujita W, Awaga K.Reversible Structural Transformation and Drastic Magnetic Change in a Copper Hydroxides Intercalation Compound [J]. J. Am. Chem. Soc., 1997, 119: 4563?4564.
[11] Fujita W, Awaga K.Intercalation of Stable Organic Radicals into Layered Copper Hydroxides [J]. Synthetic. Met., 2001, 122: 569?572.
[12] Luo Y H, Huang J G, Jin J A, et al.Formation of Positively Charged Copper Hydroxide Nanostrands and Their Structural Characterization [J]. Chem. Mater., 2006, 18: 1795?1802.
[13] Zhou S H, Feng X, Shi H Y, et al.Direct Growth of Vertically Aligned Arrays of Cu(OH)2 Nanotubes for the Electrochemical Sensing of Glucose [J]. Sensor Actuat. B-chem., 2013, 177: 445?452.
[14]王成,刘峰,叶明富,等.纳米氢氧化铜制备研究进展[J].安徽工业大学学报自然科学版, 2015, 32(02):127-132
[15]Wang C, Liu F, Ye F M, et, al.Research Progress in Preparation of Copper Hydroxide Nanomaterials[J].J. of Anhui University of Technology(Natural Science), 2015, 32(02):127-132
[16] Wang W Z, Varghese O K, Ruan C M, et al.Synthesis of CuO and Cu2O Crystalline Nanowires Using Cu(OH)2 Nanowire Templates [J]. J. Mater. Res., 2003, 18: 2756?2759.
[17] Lu C H, Qi L M, Yang J H, et al.Simple Template-free Solution Route for the Controlled Synthesis of Cu(OH)2 and CuO Nanostructures [J]. J. Phys. Chem. B, 2004, 108: 17825?17831.
[18] Wen X G, Zhang W X, Yang S H.Solution Phase Synthesis of Cu(OH)2 Nanoribbons by Coordination Self-assembly Using Cu2S Nanowires as Precursors [J]. Nano Lett., 2002, 2: 1397?1401.
[19] Giannakoudakis D A, Jiang M Y, Bandosz T J.Highly Efficient Air Desulfurization on Self-Assembled Bundles of Copper Hydroxide Nanorods [J]. ACS Appl. Mater. Inter., 2016, 8: 31986?31994.
[20] Dashamiri S, Ghaedi M, Asfaram A, et al.Multi-response Optimization of Ultrasound Assisted Competitive Adsorption of Dyes onto Cu(OH)2-nanoparticle Loaded Activated Carbon: Central Composite Design [J]. Ultrason. Sonochem., 2017, 34: 343?353.
[21] Lee S, Park S, Jeong H, et al.Effects of Post-annealing Treatment on the Microstructural Evolution and Quality of Cu(OH)2 Nanowires [J]. J. Alloy. Compd., 2015, 652: 153?157.
[22] Sun Y Z, Ma L, Zhou B B, et al.Cu(OH)2 and CuO Nanotube Networks from Hexaoxacyclooctadecane-like Posnjakite Microplates. Synthesis and Electrochemical Hydrogen Storage [J]. Int. J. Hydrogen Energ., 2012, 37: 2336?2343.
[23] Wen X G, Zhang W X, Yang S H.Synthesis of Cu(OH)2 and CuO Nanoribbon Arrays on a Copper Surface [J]. Langmuir, 2003, 19: 5898?5903.
[24] Zhang W X, Wen X G, Yang S H, et al.Single-crystalline Scroll-type Nanotube Arrays of Copper Hydroxide Synthesized at Room Temperature [J]. Adv Mater, 2003, 15: 822?825.
[25] Cheng J, Sun Y F, Zhao A, et al.Preparation of Gradient Wettability Surface by Anodization Depositing Copper Hydroxide on Copper Surface [J]. T. Nonferr. Metal Soc., 2015, 25: 2301?2307.
[26] Rodriguez-Clemente R, Serna C J, Ocana M, et al.The Relationship of Particle Morphology and Structure of Basic Copper(II) Compounds Obtained by Homogeneous Precipitation [J]. J. Cryst. Growth, 1994, 143: 277?286.
[27] Cheng Z P, Chu X Z, Zhong H, et al.Morphology Control of Cu(OH)2 Nanowire Bundles via a Simple Template-free Route [J]. Mater. Lett., 2013, 90: 41?44.
[28] Durand-keklikian L, Matijevic E.Needle-type Colloidal Copper(II) Hydroxide Particles [J]. Colloid Polym. Sci., 1990, 268: 1151?1158.
[29] Gao P, Zhang M L, Niu Z Y, et al.A facile Solution-chemistry Method for Cu(OH)2 Nanoribbon Arrays with Noticeable Electrochemical Hydrogen Storage Ability at Room Temperature. Chem. Commun., 2007, (48): 5197?5199.
[30] Park I Y, Kuroda K, Kato C.Preparation of Complex Copper-aluminum Double Hydroxide Phases from Copper (II) Ammine Complex Solutions [J]. Solid State Ionics, 1990, 42: 197?203.
[31] Falk M.The Frequency of The H-O-H Bending Fundamental in Solids and Liquids [J]. Spectrochim. Acta A., 1984, 40: 43?48.
[32] Yin A Y, Guo X Y, Dai W L, et al.The Nature of Active Copper Species in Cu-HMS Catalyst for Hydrogenation of Dimethyl Oxalate to Ethylene Glycol: New Insights on the Synergetic Effect between Cu-0 and Cu+ [J]. J. Phys. Chem. C, 2009, 113: 11003?11013.
[33] Toupance T, Kermarec M, Lambert J F, et al.Conditions of Formation of Copper Phyllosilicates in Silica-supported Copper Catalysts Prepared by Selective Adsorption [J]. J. Phys. Chem. B, 2002, 106: 2277?2286.
[34] Frost R L, Martens W, Kloprogge J T, et al.Raman Spectroscopy of the Basic Copper Chloride Minerals Atacamite and Paratacamite: Implications for the Study of Copper, Brass and Bronze Objects of Archaeological Significance [J]. J. Raman Spectrosc., 2002, 33: 801?806.
[35] Ellis T H, Wang H.Isolating the Reaction Steps in the Formation of Methoxy on Cu(100) [J]. Langmuir, 1994, 10: 4083?4088.
[36]梅德清,赵翔,王书龙,等.柴油机排放颗粒物的热重特性分析[J].农业工程学报, 2013, 29(16):50-56
[37]Mei D Q, Zhao X, Wang S L, et al.Thermogravimetric Characteristics Analysis of Particulate Matter of Emission of Divided Diesel[J].Transactions of the Chinese Society of Agricultural Engineering, 2013, 29(16):50-56